JP2000319226A - Preparation of tertiary alcohol organic carboxylate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method preparing a tertiary alcohol organic carboxylate in a single step reaction process in high yield and economic efficiency. SOLUTION: A 4-30C tertiary alcohol and a 2-18C organic carboxylic acid and 2-36C acid anhydride are reacted in the presence of a 3-54C amine compound in the preparative method. The 4-30C tertiary alcohol is preferably 1-alkyl-1- cyclohexanol. The preferable 3-54C amine is triethylamine. The preferable 2-18C organic carboxylic acid is an α,β-unsaturated carboxylic acid. The preferable 2-36C acid anhydride is propionic anhydride.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a tertiary alcohol organic carboxylic acid ester.

[0002]

2. Description of the Related Art Conventionally, primary and secondary alcohols have excellent reactivity with respect to ester synthesis, and easily react with a target organic carboxylic acid by using an acid catalyst or an alkali catalyst, Produces organic carboxylic esters. However, tertiary alcohols other than t-butanol have poor reactivity with respect to ester synthesis, and do not react with a target organic carboxylic acid even when an acid catalyst or an alkali catalyst is used. (4th edition Experimental Chemistry Lecture 22 "Organic Synthesis IV"-Acids, Amino Acids, and Peptides-, pp. 43-49, Maruzen Co., Ltd., Heisei 4)
November 30, 2003). Of the tertiary alcohols, t-
It is known that butanol reacts with a target organic carboxylic acid by adding trifluoroacetic anhydride as a dehydrating agent to produce a t-butyl organic carboxylic acid ester [R. C. Parish a
nd L. M. Stock, J.M. Org. Chem. ,
30, 927 (1965)]. On the other hand, 1-methyl-1-
As a method for producing an organic carboxylic acid ester of a tertiary alcohol represented by cyclohexanol, 1-ethyl-1-cyclohexanol, dihydro-4-terpineol and the like, tertiary alcohols and (meth) acrylic acid chlorides and the like can be used. The reaction of organic carboxylic acid chlorides or tertiary alcohols with carboxylic acid anhydrides such as (meth) acrylic anhydride has been known for a long time (4th edition Experimental Chemistry Lecture 22 “Organic Synthesis IV” -Acid. Amino acids / peptides, pp. 50-51, Maruzen Co., Ltd., issued on November 30, 1992).

[0003] However, organic carboxylic acid chlorides such as (meth) acrylic acid chloride are very expensive and difficult to handle due to unstable physical properties. When decomposed, hydrogen chloride is generated and adversely affects the global environment. There is a problem of giving. Further, in the method using a carboxylic anhydride such as (meth) acrylic anhydride, the carboxylic anhydride to be used is very expensive, and further, a carboxylic acid such as (meth) acrylic acid is used as a by-product of the reaction. It has various disadvantages, such as the release of one molecule and the difficulty in converting this carboxylic acid to the anhydride for reuse.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a novel process for economically producing a tertiary alcohol organic carboxylic acid ester in a one-step reaction process in a high yield. .

The present inventors have studied an economical method for producing an organic carboxylic acid ester of a tertiary alcohol, and have intensively studied to solve the conventional problems. Are reacted with inexpensive organic carboxylic acids and carboxylic anhydrides in the presence of an amine compound having a specific number of carbon atoms, whereby a tertiary alcohol organic carboxylic acid ester can be economically synthesized in high yield. Thus, the method of the present invention has been completed.

[0006]

According to the present invention, there is provided a compound having 4 to 3 carbon atoms.
A tertiary alcohol having 0 to 3 carbon atoms and a carboxylic acid anhydride having 2 to 36 carbon atoms in the presence of an amine compound having 3 to 54 carbon atoms. It is intended to provide a method for producing a tertiary alcohol organic carboxylic acid ester. Here, the carbon number 4
The -30 tertiary alcohol is preferably 1-alkyl-1-cyclohexanol or dihydro-4-terpineol. The amine compound having 3 to 54 carbon atoms is preferably triethylamine. Further, the organic carboxylic acid having 2 to 18 carbon atoms is preferably an α, β-unsaturated carboxylic acid (meth) acrylic acid and crotonic acid, particularly preferably acrylic acid and crotonic acid. Further, the carboxylic anhydride having 2 to 36 carbon atoms is preferably acetic anhydride or propionic anhydride.

[0007]

DETAILED DESCRIPTION OF THE INVENTION The raw materials used in the present invention are tertiary alcohols having 4 to 30 carbon atoms, amine compounds having 3 to 54 carbon atoms, organic carboxylic acids having 2 to 18 carbon atoms, and 2 to 36 carbon atoms. The carboxylic acid anhydride does not need to be particularly purified, and the one having a general reagent purity may be used as it is.

The raw material used in the present invention has 4 to 4 carbon atoms.
30 tertiary alcohols include t-butanol, 2-methyl-2-butanol, 2-methyl-2-hexanol, 3-ethyl-3-pentanol, 2,6-dimethylheptanol, and 2-methyl- 3-buten-2-ol,
Ambrinol, 1-alkyl-1-cyclohexanol such as 1-methyl-1-cyclohexanol and 1-ethyl-1-cyclohexanol, 1-adamantanol, 2-methyl-2-adamantanol, α-terpineol, β-terpineol, γ-terpineol, 1
-Terpineol, dihydro-α-terpineol, dihydro-β-terpineol, dihydro-γ-terpineol, dihydro-1-terpineol, 4-tuanol, nerolidol, aloocimenol, myrcenol,
Dihydromyrcenol, tetrahydromyrcenol, oximenol, 3,6-dimethyl-3-octanol, linalool, ethyl linalool, dihydro linalool, tetrahydro linalool, 2-pinanol, 4-terpineol, dihydro-4-terpineol, cedrol,
α-Bisabolol, β-bisabolol, β-caryophyllene alcohol, patchouli alcohol, isophytol, geranyl linalool, sclareol, and the like. Preferably, they are 1-alkyl-1-cyclohexanol and dihydro-4-terpineol. However, the tertiary alcohol of the present invention is not limited only to these. Here, the carbon number of the tertiary alcohol is 4 to 30, preferably 4 to 15. Carbon number 3
The following are not present in tertiary alcohols. On the other hand, when the number of carbon atoms is 31 or more, the molecular weight is too large, the reactivity is low,
Sufficient yield cannot be obtained.

The raw material amine compound having 3 to 54 carbon atoms used in the present invention includes triethylamine, pyridine, dimethylaniline, 4-dimethylaminopyridine, 4-pyrrolidinopyridine, diazabicycloundecene and the like. Can be Preferably it is triethylamine. However, the amine compound of the present invention is not limited to only these amine compounds. The amine compound has 3 to 54 carbon atoms, preferably 3 to 24 carbon atoms, and more preferably 6 to 12 carbon atoms. When the number of carbon atoms is 1 or 2, the boiling point is low and it is difficult to handle. On the other hand, when the carbon number is 55 or more, the molecular weight is too large, the reactivity is low, and a sufficient yield cannot be obtained.

Further, examples of the organic carboxylic acid having 2 to 18 carbon atoms as a raw material used in the present invention include acetic acid, propionic acid, acrylic acid, methacrylic acid, crotonic acid, benzoic acid, cinnamic acid, linoleic acid and the like. Can be Acrylic acid, methacrylic acid, crotonic acid and cinnamic acid which are α, β-unsaturated carboxylic acids are preferred, and acrylic acid and crotonic acid are more preferred. However, the organic carboxylic acid of the present invention is not limited to only these organic carboxylic acids. The organic carboxylic acid has 2 to 18 carbon atoms, preferably 3 to 7 carbon atoms. Carbon number 19
Above, the molecular weight is too large, the reactivity is low, and a sufficient yield cannot be obtained.

The raw materials used in the present invention include carboxylic anhydrides having 2 to 36 carbon atoms, such as acetic anhydride, propionic anhydride, butyric anhydride, phthalic anhydride, maleic anhydride, itaconic anhydride and citraconic anhydride. and so on. Preferred are acetic anhydride, propionic anhydride, butyric anhydride, phthalic anhydride, and maleic anhydride, and more preferred are acetic anhydride and propionic anhydride. However, the organic carboxylic anhydride of the present invention is not limited to only these organic carboxylic anhydrides. In the carboxylic anhydride, there is no carboxylic anhydride having 1 carbon atom. On the other hand, if the number of carbon atoms is 37 or more, the molecular weight is too large, the reactivity is low, and a sufficient yield cannot be obtained.

In the present invention, a tertiary alcohol having 4 to 30 carbon atoms, an amine compound having 3 to 54 carbon atoms,
The reaction for synthesizing a tertiary alcohol organic carboxylic acid ester from an organic carboxylic acid having from 18 to 18 or a carboxylic anhydride having from 2 to 36 carbon atoms can be carried out under any conditions of normal pressure, reduced pressure, and increased pressure. It is. The reaction system is not particularly limited, and it can be carried out in a continuous system, a batch system, or a semi-batch system.

In practicing the present invention, a polymerization inhibitor may be added to the reaction system. Specifically, examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, and phenothiazine. Preferably, they are hydroquinone, phenothiazine and the like, but the present invention is not limited to these polymerization inhibitors.

In practicing the present invention, a polymerization inhibitor,
A solvent inert to the raw materials and products may be added. Specifically, n-butane, n-pentane, n-hexane, n-heptane, aliphatic saturated hydrocarbons such as n-octane, benzene, toluene, aromatic hydrocarbons such as xylene and the like, a solvent or Although it can be used as a diluent, the present invention is not limited to these.

In carrying out the present invention, a tertiary alcohol having 4 to 30 carbon atoms, an amine compound having 3 to 54 carbon atoms, an organic carboxylic acid having 2 to 18 carbon atoms, and a C2 to 36 carbon atoms to be subjected to the reaction. The charge ratio of the carboxylic acid anhydride is not particularly limited, but the molar ratio of the amine compound having 3 to 54 carbon atoms / the tertiary alcohol having 4 to 30 carbon atoms is preferably in the range of 0.1 to 100 in terms of molar ratio. preferable. More preferably, it is in the range of 0.5 to 50, particularly preferably 0.6 to 30. If the charge ratio is less than 0.1 (molar ratio),
When the progress of the reaction is slow, on the other hand, when it exceeds 100 (molar ratio), the reaction proceeds sufficiently, but it is not preferable from an economic viewpoint.

Further, an organic carboxylic acid having 2 to 18 carbon atoms /
The molar ratio of the tertiary alcohol having 4 to 30 carbon atoms is preferably in the range of 0.1 to 100 in terms of molar ratio, more preferably 0.5 to 50, and particularly preferably 0.6 to 30. is there. When the charge ratio is less than 0.1 (molar ratio), the progress of the reaction slows down. On the other hand, when the charge ratio exceeds 100 (molar ratio), the reaction proceeds sufficiently but is not preferable from an economic viewpoint.

The molar ratio of the carboxylic anhydride having 2 to 36 carbon atoms to the tertiary alcohol having 4 to 30 carbon atoms is preferably in the range of 0.1 to 100 in terms of molar ratio, more preferably 0 to 100. 0.5 to 50, particularly preferably 0.6 to 30. If the charge ratio is less than 0.1 (molar ratio),
When the progress of the reaction is slow, on the other hand, when it exceeds 100 (molar ratio), the reaction proceeds sufficiently, but it is not preferable from an economic viewpoint.

In carrying out the present invention, there are no particular restrictions on the method of charging the raw materials and the like, and the amine compound has 3 to 54 carbon atoms, an organic carboxylic acid having 2 to 18 carbon atoms, and a carboxylic acid having 2 to 36 carbon atoms. An anhydride and a tertiary alcohol having 4 to 30 carbon atoms may be simultaneously charged, and before the reaction, an amine compound having 3 to 54 carbon atoms and an organic carboxylic acid having 2 to 18 carbon atoms are mixed beforehand. A method of adding a tertiary alcohol having 4 to 30 carbon atoms, and a tertiary alcohol having 4 to 30 carbon atoms, an amine compound having 3 to 54 carbon atoms, and a carboxylic anhydride having 2 to 36 carbon atoms were previously mixed. Thereafter, a method such as adding an organic carboxylic acid having 2 to 18 carbon atoms can also be carried out.

In the present invention, the reaction temperature for carrying out the reaction is not particularly limited, and it is possible to carry out the reaction in a wide temperature range, but it is usually in the range of 0 to 300 ° C., preferably 20 to 150 ° C. And more preferably 40 to 120.
C., particularly preferably at 70 to 90.degree. If the reaction is carried out at a temperature lower than 0 ° C., the reaction rate decreases,
On the other hand, if the reaction is carried out at a temperature exceeding 300 ° C., the thermal stability of the raw material is lowered, polymerization is caused, and it is not economical. The reaction time depends on the reaction temperature, but is short for a high temperature and long for a low temperature. Usually 70-90 ° C
For 2 to 18 hours. After completion of the reaction, the desired product can be obtained by a separation operation such as a normal distillation operation.

The following three methods can be given as specific embodiments for carrying out the present invention, but the present invention is not limited to these three methods. (1) A predetermined amount of a tertiary alcohol, an amine compound, an organic carboxylic acid and a carboxylic anhydride in a glass flask equipped with a stirrer and a reflux condenser, if necessary, a polymerization inhibitor, a solvent, etc. And heat-stirring reaction. (2) a predetermined amount of tertiary alcohol in an autoclave,
A method in which an amine compound, an organic carboxylic acid, and a carboxylic anhydride are added together with a polymerization inhibitor, if necessary, and an inert medium such as nitrogen or argon, followed by a heating and stirring reaction. (3) Predetermined amounts of a tertiary alcohol, an amine compound, an organic carboxylic acid and a carboxylic anhydride in a reactor previously maintained at a predetermined temperature and a predetermined pressure, if necessary, a polymerization inhibitor, a solvent, etc. A method of continuously introducing a diluent together with a diluent to carry out the reaction.

After completion of the reaction, the desired product is isolated from the reaction mixture, for example, as follows. After washing the reaction solution after completion of the reaction with an aqueous solution of sodium hydrogen carbonate and water, low-boiling components are removed under reduced pressure, whereby a high-purity crude product can be obtained in high yield. If necessary, the crude product is distilled under reduced pressure to obtain a product with higher purity.

In particular, among the tertiary alcohol organic carboxylic acid esters obtained, (meth) acrylic acid esters have high polymerizability, so that it is preferable to carry out distillation in as short a time as possible. During the reaction / distillation, a polymerization inhibitor may be added. Hydroquinone,
Hydroquinone monomethyl ether, methylhydroquinone, phenothiazine and the like can be mentioned, and these can be used alone or in combination of two or more.

Examples of the tertiary alcohol organic carboxylic acid ester prepared according to the present invention include 1-methyl-1-cyclohexyl acrylate or methacrylate, 1-ethyl-1-cyclohexyl acrylate or methacrylate and dihydro-4-methacrylate. Examples include terpinyl acrylate or methacrylate. 1
-Methyl-1-cyclohexyl acrylate is represented by the following chemical formula (1) [general formula (I)], and 1-methyl-1-cyclohexyl methacrylate is represented by the following chemical formula (2) [general formula (II)]
And 1-ethyl-1-cyclohexyl acrylate is represented by the following formula (III) [general formula (III)], and 1-ethyl-1-cyclohexyl methacrylate is represented by the following formula (III) [general formula (I)
V)], dihydro-4-terpinyl acrylate is represented by the following formula (5) [general formula (V)], and dihydro-4-terpinyl methacrylate is represented by the following formula (6) [general formula (VI)].
And each has the structure shown.

[0024]

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[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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The tertiary alcohol organic carboxylic acid ester produced according to the present invention comprises a polymer material, a polymer raw material,
Polymer modifiers, fragrances, developers, antistatic agents, antioxidants, ultraviolet absorbers, detergents, surfactants, emulsifiers, insecticides, pesticides, fungicides, repellents, herbicides, dyes, pharmaceuticals, Rubber chemicals, stabilizers, colorants, flame retardants, plasticizers, crystal nucleating agents, compatibilizers, lubricants, curing agents, tanning agents, adhesives, tackifiers, tackifiers, modifiers, binders , Oils and fats, paints,
Paint modifiers, traffic paints, inks, ink modifiers, toners, sizing agents, sizing agents, rubber modifiers, fiber treatment agents, photocurable reactive diluents, crosslinkers, plasticizers, paper coating agents, ultraviolet rays -Used as a raw material or material for electron beam curable monomers, photoresists, etc.

The process for producing a tertiary alcohol organic carboxylic acid ester of the present invention is very expensive,
This method is a one-stage reaction process and economical production with high yield without using acid chloride which is unstable and causes environmental pollution problems as a raw material. The manufactured tertiary alcohol organic carboxylic acid ester is used not only as a material for high-performance photoresist used in microfabrication in the manufacturing process of semiconductor devices, but also useful for polymer materials, optical materials, paints, etc. is there. In particular, (meth) acrylic acid esters are particularly useful as polymer materials such as photoresists for KrF and ArF excimer lasers, optical materials, UV inks, UV paints, and coating agents.

[0032]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to Examples, but the present invention is not limited thereto. Parts and% in Examples and Comparative Examples are based on weight unless otherwise specified. The product was identified by boiling point and infrared absorption spectrum analysis (measured by FTIR-8100M, manufactured by Shimadzu Corporation).

Example 1 2,000 ml equipped with a stirrer and a reflux condenser
296.9 g (4.0) of acrylic acid in a four-necked flask of
Mol, purity 97%), acetic anhydride 206.0 g (2.0 mol, purity 99%), triethylamine 306.0 g
(3.0 mol, purity 99%) and 130.6 g of 1-ethyl-1-cyclohexanol (1.0 mol, purity 98)
%), And the mixture was heated and stirred at 70 ° C. for 12 hours to carry out a reaction. After cooling, the reaction solution was poured into n-hexane, and 5%
After washing twice with an aqueous solution of sodium hydrogen carbonate and twice with tap water,
By performing distillation under reduced pressure, 126.3 g of 1-ethyl-1-cyclohexyl acrylate (boiling point: 65 ° C./3 mmH
g, 6 based on 1-ethyl-1-cyclohexanol
8%, purity 98%). FIGS. 1 and 2 show IR charts of 1-ethyl-1-cyclohexanol used as a raw material and 1-ethyl-1-cyclohexyl acrylate obtained.

Example 2 2,000 ml equipped with a stirrer and a reflux condenser
351.0 g of crotonic acid (4.0
Mol, purity 98%), acetic anhydride 206.0 g (2.0 mol, purity 99%), triethylamine 306.0 g
(3.0 mol, purity 99%) and 130.6 g of 1-ethyl-1-cyclohexanol (1.0 mol, purity 98)
%), And the mixture was heated and stirred at 80 ° C. for 12 hours to carry out a reaction. After cooling, the reaction solution was poured into n-hexane, and 5%
After washing twice with an aqueous solution of sodium hydrogen carbonate and twice with tap water,
By distillation under reduced pressure, 136.6 g of 1-ethyl-1-cyclohexylcrotonate (boiling point: 72 ° C./3 mmH
g, 6 based on 1-ethyl-1-cyclohexanol
9%, purity 98%).

Example 3 2,000 ml equipped with a stirrer and a reflux condenser
305.2 g of propionic acid in a four-necked flask
(4.0 mol, purity 97%) and 206.0 g of acetic anhydride
(2.0 mol, purity 99%), triethylamine 30
6.0 g (3.0 mol, purity 99%) and 130.6 g of 1-ethyl-1-cyclohexanol (1.0 mol,
(Purity: 98%), and the mixture was heated and stirred at 90 ° C. for 20 hours to carry out a reaction. After cooling, the reaction solution was poured into n-hexane, washed twice with a 5% aqueous sodium hydrogen carbonate solution and twice with tap water, and distilled under reduced pressure to give 1-ethyl-1-cyclohexylpropionate 94. 8g (boiling point 67 ° C /
3 mmHg, 50% yield and 97% purity based on 1-ethyl-1-cyclohexanol).

Example 4 2,000 ml equipped with a stirrer and a reflux condenser
Benzoic acid 498.0 g (4.0
Mol, purity 98%), acetic anhydride 206.0 g (2.0 mol, purity 99%), triethylamine 306.0 g
(3.0 mol, purity 99%) and 130.6 g of 1-ethyl-1-cyclohexanol (1.0 mol, purity 98)
%), And the mixture was heated and stirred at 90 ° C. for 12 hours to carry out a reaction. After cooling, the reaction solution was poured into n-hexane, and 5%
After washing twice with an aqueous solution of sodium hydrogen carbonate and twice with tap water,
By vacuum distillation, 132.6 g of 1-ethyl-1-cyclohexylbenzoate (boiling point: 98 ° C./3 mmH
g, yield 5 based on 1-ethyl-1-cyclohexanol
6%, purity 98%).

Example 5 2,000 ml equipped with a stirrer and a reflux condenser
296.9 g of acrylic acid (4.
0 mol, purity 97%), hydroquinone 0.3 g, acetic anhydride 206.0 g (2.0 mol, purity 99%), triethylamine 306.0 g (3.0 mol, purity 99%) and 1-ethyl-1- 130.6 g of cyclohexanol
(1.0 mol, purity 98%) was added, and the mixture was heated and stirred at 80 ° C. for 8 hours to carry out a reaction. After cooling, the reaction solution was poured into n-hexane, and added with a 5% aqueous sodium hydrogen carbonate solution.
1 time by washing twice with tap water and then vacuum distillation.
148.6 g of ethyl-1-cyclohexyl acrylate
(Boiling point 65 ° C./3 mmHg, yield 80% based on 1-ethyl-1-cyclohexanol, purity 98%).

Example 6 2,000 ml equipped with a stirrer and a reflux condenser
354.6 g of methacrylic acid in a four-necked flask
(4.0 mol, purity 97%), hydroquinone 0.3
g, acetic anhydride 206.0 g (2.0 mol, purity 99)
%), 306.0 g (3.0 mol, purity 99%) of triethylamine and 130.6 g (1.0 mol, 98% purity) of 1-ethyl-1-cyclohexanol were added, and 80
The mixture was heated and stirred at 8 ° C. for 8 hours to carry out the reaction. After cooling, the reaction solution was poured into n-hexane, washed twice with a 5% aqueous sodium hydrogen carbonate solution and twice with tap water, and then distilled under reduced pressure to obtain 76.0 g of 1-ethyl-1-cyclohexyl methacrylate ( Boiling point 75 ° C / 3mmHg, 1-ethyl-1
-Yield 38%, purity 98% based on cyclohexanol)
I got

Example 7 2,000 ml equipped with a stirrer and a reflux condenser
296.9 g of acrylic acid (4.
0 mol, purity 97%), phenothiazine 0.3 g, acetic anhydride 206.0 g (2.0 mol, purity 99%), triethylamine 306.0 g (3.0 mol, purity 99%) and 1-methyl-1- 116.3 g of cyclohexanol
(1.0 mol, 98% purity), and the mixture was heated and stirred at 85 ° C. for 8 hours to carry out a reaction. After cooling, the reaction solution was poured into n-hexane, and added with a 5% aqueous sodium hydrogen carbonate solution.
1 time by washing twice with tap water and then vacuum distillation.
142.8 g of methyl-1-cyclohexyl acrylate
(Boiling point 60 ° C./3 mmHg, yield 85% based on 1-methyl-1-cyclohexanol, purity 98%).

Example 8 2,000 ml equipped with a stirrer and a reflux condenser
296.9 g of acrylic acid (4.
0 mol, purity 97%), hydroquinone 0.3 g, acetic anhydride 206.0 g (2.0 mol, purity 99%), triethylamine 306.0 g (3.0 mol, purity 99%) and dihydro-4-terpineol 159 .2 g (1.
(0 mol, 98% purity), and the mixture was heated and stirred at 90 ° C. for 12 hours to carry out a reaction. After cooling, the reaction solution was poured into n-hexane, washed twice with a 5% aqueous sodium hydrogen carbonate solution and twice with tap water, and then distilled under reduced pressure to obtain dihydro-
150.0 g of 4-terpinel acrylate (80 ° C. boiling point)
/ 3 mmHg, 70% yield based on dihydro-4-terpineol, purity 98%).

Example 9 2,000 ml equipped with a stirrer and a reflux condenser
296.9 g of acrylic acid (4.
0 mol, purity 97%), hydroquinone 0.3 g, propionic anhydride 265.3 g (2.0 mol, purity 98)
%), 306.0 g (3.0 mol, purity 99%) of triethylamine and 130.6 g (1.0 mol, 98% purity) of 1-ethyl-1-cyclohexanol were added, and 80
The mixture was heated and stirred at 8 ° C. for 8 hours to carry out the reaction. After cooling, the reaction solution was poured into n-hexane, washed twice with a 5% aqueous sodium hydrogen carbonate solution and twice with tap water, and then distilled under reduced pressure to obtain 1-ethyl-1-cyclohexyl acrylate 1.
44.9 g (boiling point 65 ° C./3 mmHg, 1-ethyl-1
-78% yield and 98% purity based on cyclohexanol)
I got

Example 10 2,000 ml equipped with a stirrer and a reflux condenser
296.9 g of acrylic acid (4.
0 mol, purity 97%), hydroquinone 0.3 g, butyric anhydride 322.4 g (2.0 mol, purity 98%), triethylamine 306.0 g (3.0 mol, purity 99%) and 1-ethyl-1- 130.6 g of cyclohexanol
(1.0 mol, purity 98%) was added, and the mixture was heated and stirred at 80 ° C. for 8 hours to carry out a reaction. After cooling, the reaction solution was poured into n-hexane, and added with a 5% aqueous sodium hydrogen carbonate solution.
1 time by washing twice with tap water and then vacuum distillation.
139.3 g of ethyl-1-cyclohexyl acrylate
(A boiling point of 65 ° C./3 mmHg, a yield of 75% based on 1-ethyl-1-cyclohexanol, and a purity of 98%) were obtained.

Example 11 2,000 ml equipped with a stirrer and a reflux condenser
296.9 g of acrylic acid (4.
0 mol, purity 97%), hydroquinone 0.3 g, phthalic anhydride 298.8 g (2.0 mol, purity 99%), triethylamine 306.0 g (3.0 mol, purity 99)
%) And 1-ethyl-1-cyclohexanol 13
0.6 g (1.0 mol, purity 98%) was added, and the mixture was heated and stirred at 86 ° C. for 12 hours to carry out a reaction. After cooling, the reaction solution was poured into n-hexane, washed twice with a 5% aqueous sodium hydrogen carbonate solution and twice with tap water, and distilled under reduced pressure to obtain 1-ethyl-1-cyclohexyl acrylate 11
1.4 g (boiling point 65 ° C./3 mmHg, 1-ethyl-1-
(Yield 60%, purity 98%) based on cyclohexanol.

Example 12 2,000 ml equipped with a stirrer and a reflux condenser
296.9 g of acrylic acid (4.
0 mol, purity 97%), hydroquinone 0.3 g, maleic anhydride 198.0 g (2.0 mol, purity 99%),
306.0 g of triethylamine (3.0 mol, purity 99)
%) And 1-ethyl-1-cyclohexanol 13
0.6 g (1.0 mol, purity 98%) was added, and the mixture was heated and stirred at 70 ° C. for 12 hours to carry out a reaction. After cooling, the reaction solution was poured into n-hexane, washed twice with a 5% aqueous sodium hydrogen carbonate solution and twice with tap water, and distilled under reduced pressure to obtain 1-ethyl-1-cyclohexyl acrylate 12.
2.6 g (boiling point 65 ° C./3 mmHg, 1-ethyl-1-
The yield was 66% based on cyclohexanol and the purity was 98%).

Comparative Example 1 2,000 ml equipped with a stirrer and a reflux condenser
296.9 g of acrylic acid (4.
0 mol, purity 97%), 306.0 g of triethylamine
(3.0 mol, purity 99%) and 130.6 g of 1-ethyl-1-cyclohexanol (1.0 mol, purity 98)
%), And the mixture was heated and stirred at 70 ° C. for 12 hours to carry out a reaction. However, after completion of the reaction, the product obtained by washing and distillation under reduced pressure is an unreacted raw material, and 1-ethyl-1
-Cyclohexyl acrylate was not obtained.

Comparative Example 2 2,000 ml equipped with a stirrer and a reflux condenser
296.9 g of acrylic acid (4.
0 mol, purity 97%), 206.0 g of acetic anhydride (2.0
Mol, purity 99%) and 130.6 g (1.0 mol, purity 98%) of 1-ethyl-1-cyclohexanol were added thereto, and the mixture was heated with stirring at 70 ° C. for 12 hours to carry out a reaction.
However, after completion of the reaction, the product obtained by washing and distillation under reduced pressure was an unreacted raw material, and 1-ethyl-1-cyclohexyl acrylate was not obtained.

Comparative Example 3 2,000 ml equipped with a stirrer and a reflux condenser
130.6 g (1.0 mol, purity 98%) of toluene 400 g, hydroquinone 0.3 g, and triethylamine 306.0 g (3.0 mol, purity 99) %) And heated to 40 ° C. with stirring, and 142.9 g (1.5 mol, 95% purity) of acrylic acid chloride was added thereto.
The reaction was carried out by dropping over time. After cooling, the reaction
% Aqueous sodium hydrogencarbonate twice and with tap water twice, and then distilled under reduced pressure to give 10.7 g of 1-ethyl-1-cyclohexyl acrylate (boiling point: 65 ° C./3 m
mHg, 65% yield and 98% purity based on 1-ethyl-1-cyclohexanol).

Comparative Example 4 A method similar to that of Comparative Example 3 was used, except that 165.0 g (1.5 mol, purity 95%) of methacrylic chloride was used instead of acrylic chloride. As a result, 1
-Ethyl-1-cyclohexyl methacrylate 130.
0 g (boiling point 75 ° C./3 mmHg, yield 65% based on 1-ethyl-1-cyclohexanol, purity 98%) was obtained.

Comparative Example 5 Instead of 1-ethyl-1-cyclohexanol, 1-
116.3 g of methyl-1-cyclohexanol (1.0
Mol, purity 98%), except that the method of Comparative Example 3 was used. As a result, 100.8 g of 1-methyl-1-cyclohexyl acrylate (boiling point: 60 ° C./3 mmH
g, yield 6 based on 1-methyl-1-cyclohexanol
0%, 98% purity).

Comparative Example 6 In place of 1-ethyl-1-cyclohexanol, 159.2 g of dihydro-4-terpineol (1.0 mol,
Except for using 98% purity), the same method as in Comparative Example 3 was used. As a result, 117.8 g of dihydro-4-terpinyl acrylate (boiling point 80 ° C./3 mmHg,
55% yield and 98% purity based on 4-terpineol).

Comparative Example 7 2,000 ml equipped with a stirrer and a reflux condenser
296.9 g of acrylic acid (4.
0 mol, purity 97%), 0.05 g of sulfuric acid as an acid catalyst,
And 13-ethyl-1-cyclohexanol 130.6
g (1.0 mol, purity 98%) was added, and the mixture was heated and stirred at 70 ° C. for 2 hours to carry out a reaction. However, 1-ethyl-1-cyclohexanol causes a dehydration reaction,
It becomes ethyl-1-cyclohexene and 1-ethyl-1-
Cyclohexyl acrylate was not obtained.

As a result of the above examples, the method for producing a tertiary alcohol organic carboxylic acid ester of the present invention is as follows.
A product having a yield of 50% or more and a purity of 97% or more was stably obtained. On the other hand, Comparative Example 1 was an example in which the carboxylic anhydride of the present invention was not present, and the target product obtained in Example 1 was not obtained. Comparative Example 2 was an example in which the amine compound of the present invention was not used, and the target product obtained in Example 1 was not obtained. In Comparative Examples 3 to 6, the organic acid chloride [(meth) acrylic acid chloride], which is much more expensive and unstable than the conventional organic carboxylic acid [(meth) acrylic acid], and the tertiary alcohol were used as amine compounds. In this example, the reaction was carried out in the presence, and almost all of the yields were lower than those of the corresponding examples. Comparative Example 7 is an example of esterification in the presence of a sulfuric acid catalyst of the conventional example, and the corresponding ester compound was not obtained in Example 1 corresponding thereto.

[0053]

According to the present invention, a tertiary alcohol having 4 to 30 carbon atoms such as 1-methyl-1-cyclohexanol, 1-ethyl-1-cyclohexanol and dihydro-4-terpineol is used. In the presence of an amine compound having 3 to 54 carbon atoms, an organic carboxylic acid having 2 to 18 carbon atoms such as inexpensive (meth) acrylic acid and a carboxylic anhydride having 2 to 36 carbon atoms such as acetic anhydride are used. React to form a tertiary alcohol organic carboxylic acid ester
It can be produced economically in a stepwise reaction process and in high yields, and its industrial value is high. The obtained tertiary alcohol organic carboxylic acid ester, especially tertiary alcohol (meth) acrylate, is used for a wide range of applications such as photoresists for KrF and ArF excimer lasers, UV inks, UV paints, coating agents and adhesives. .

[Brief description of the drawings]

FIG. 1 is an IR chart of 1-ethyl-1-cyclohexanol used in Example 1.

FIG. 2 is an IR chart of 1-ethyl-1-cyclohexyl acrylate obtained in Example 1.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Toshiyuki Morikawa 1080, Takagi-cho, Fuchu-shi, Hiroshima F-term in Yasharake Mical Co., Ltd. 4H006 AA02 AB76 AB84 AC48 BA51 BA69 BA92 BA94 BB61 BC10 BC19 BC31 BC34 BT14

Claims (10)

[Claims] 1. A tertiary alcohol having 4 to 30 carbon atoms,
In the presence of an amine compound having 3 to 54 carbon atoms, 2 to 1 carbon atoms
8. A method for producing an organic carboxylic acid ester of a tertiary alcohol, which is reacted with an organic carboxylic acid of No. 8 and a carboxylic anhydride having 2 to 36 carbon atoms. 2. A tertiary alcohol having 4 to 30 carbon atoms is 1
The method for producing a tertiary alcohol organic carboxylic acid ester according to claim 1, which is -alkyl-1-cyclohexanol. 3. The method according to claim 1, wherein the tertiary alcohol having 4 to 30 carbon atoms is dihydro-4-terpineol. 4. The method for producing a tertiary alcohol organic carboxylic acid ester according to claim 1, wherein the amine compound having 3 to 54 carbon atoms is triethylamine. 5. An organic carboxylic acid having 2 to 18 carbon atoms is α,
The method for producing a tertiary alcohol organic carboxylic acid ester according to claim 1, which is a β-unsaturated carboxylic acid. 6. The method for producing a tertiary alcohol organic carboxylic acid ester according to claim 1, wherein the organic carboxylic acid having 2 to 18 carbon atoms is (meth) acrylic acid. 7. The method for producing a tertiary alcohol organic carboxylic acid ester according to claim 1, wherein the organic carboxylic acid having 2 to 18 carbon atoms is acrylic acid. 8. The method for producing a tertiary alcohol organic carboxylic acid ester according to claim 1, wherein the organic carboxylic acid having 2 to 18 carbon atoms is crotonic acid. 9. The method for producing a tertiary alcohol organic carboxylic acid ester according to claim 1, wherein the carboxylic anhydride having 2 to 36 carbon atoms is acetic anhydride. 10. The method for producing a tertiary alcohol organic carboxylic acid ester according to claim 1, wherein the carboxylic anhydride having 2 to 36 carbon atoms is propionic anhydride.